CN104471103B - Sputtering target, oxide semiconductor thin film, and method for producing same - Google Patents

Sputtering target, oxide semiconductor thin film, and method for producing same Download PDF

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Publication number
CN104471103B
CN104471103B CN201380037627.8A CN201380037627A CN104471103B CN 104471103 B CN104471103 B CN 104471103B CN 201380037627 A CN201380037627 A CN 201380037627A CN 104471103 B CN104471103 B CN 104471103B
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sputtering
target
oxide
sputtering target
manufacture method
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CN104471103A (en
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江端晃
江端一晃
西村麻美
但马望
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Idemitsu Kosan Co Ltd
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Idemitsu Kosan Co Ltd
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    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
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    • C04B35/453—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates
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Abstract

The invention provides a sputtering target, which is composed of an oxide containing indium element (In), tin element (Sn), zinc element (Zn) and aluminum element (A1), and comprises InAlO3(ZnO)m(m is 0.1 to 10) and the atomic ratio of the indium element, the tin element, the zinc element and the aluminum element satisfies specific requirements.

Description

Sputtering target, oxide semiconductor thin-film and their manufacture method
Technical field
The present invention relates to sputtering target, oxide semiconductor thin-film and their manufacture method.
Background technology
The FETs such as thin film transistor (TFT) (TFT) are by the per-unit electronics unit as semiconductor integrated circuit memory Part, high-frequency signal amplifier element, liquid crystal drive element etc. are widely used, and are now by the electronics device of practical application most Part.Wherein, with the significant development of display device in recent years, in liquid crystal display device (LCD), el display device (EL), in the various display devices such as Field Emission Display (FED), display is driven to fill as driving voltage is applied to display element The switch element put, largely uses TFT.
As the material of the semiconductor layer (channel layer) of the main member for belonging to FET, silicon semiconductor chemical combination Thing obtains most commonly used use.In general, needing High frequency amplification element, integrated circuit element of working at high speed etc. In, use silicon single crystal.On the other hand, in liquid crystal drive element etc., amorphism silicon is used due to the requirement of large area Semiconductor (amorphous silicon).
The film of amorphous silicon can be formed at a lower temperature, but switching speed is slow compared with crystalline film, Therefore when being used as the switch element of driving display device, the situation that the animation of high speed shows that cannot follow is had.Specifically For, for resolution ratio is for the LCD TV of VGA, it is possible to use mobility is 0.5~1cm2The amorphous silicon of/Vs, and such as Fruit resolution ratio be SXGA, UXGA, QXGA or its more than, then require 2cm2The mobility of/more than Vs.In addition, when in order to improve picture Matter and during improve improve frequency, it is necessary to mobility higher.
On the other hand, although crystalline silicon based thin film mobility is high, but very big energy is needed when there are manufacture And the problems such as process number or it is difficult to the problem of large area.For example, needing more than 800 DEG C when silicon based thin film is crystallized High temperature or the laser annealing using expensive equipment.In addition, the element of the crystalline usual TFT of silicon based thin film is constituted being defined It is that top-gated is constituted, the cost such as the reduction reduction therefore, it is difficult to realize mask sheet number.
In order to solve this kind of problem, studied and used the oxide formed by indium oxide, zinc oxide and gallium oxide partly to lead The thin film transistor (TFT) of body film.In general, the making of oxide semiconductor thin-film is to utilize to have used comprising oxidate sintered body The sputtering of target (sputtering target) carry out.
For example, as it is known that having comprising with formula In2Ga2ZnO7、InGaZnO4The chemical combination for showing homology crystal structure for representing The target (patent document 1,2 and 3) of thing.But, in order to improve sintered density (relative density), it is necessary in oxidizing atmosphere in the target Sintering, and in this case, in order to reduce the resistance of target, the reduction treatment under high temperature is needed after sintering.In addition, if when long Between use target, will the characteristic of rewarding film, film forming speed be widely varied, cause by In2Ga2ZnO7、InGaZnO4It is different The problems such as often having the generation of particle when being frequently grown the paradoxical discharge, the film forming that cause.If continually there is paradoxical discharge, etc. Plasma discharge state will be unstable, it is impossible to the film forming stablized, and membrane property is had undesirable effect.
On the other hand, it is also proposed that cross to have used and do not contain gallium and the amorphous oxide semiconductor comprising indium oxide and zinc oxide The thin film transistor (TFT) (patent document 4) of film.But there is following problem, i.e. if partial pressure of oxygen when not improving film forming, just cannot Realize normal pass (normally-off) running of TFT.
In addition, also studying in the In using tin oxide as principal component2O3-SnO2In-ZnO systems oxide containing Ta or Y, The protective layer used sputtering target (patent document 5 and 6) of the optical information recording medium of the addition element of Si etc.But, these targets Not oxide semiconductor purposes, in addition, easily forming the agglomerate of insulating properties material, there are resistance value and uprises, easily draws Play the problem of paradoxical discharge.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 8-245220 publications
Patent document 2：Japanese Unexamined Patent Publication 2007-73312 publications
Patent document 3：No. 2009/084537 pamphlet of International Publication No.
Patent document 4：No. 2005/088726 pamphlet of International Publication No.
Patent document 5：No. 2005/078152 pamphlet of International Publication No.
Patent document 6：No. 2005/078153 pamphlet of International Publication No.
The content of the invention
It is an object of the present invention to provide a kind of high density and low-resistance sputtering target.
Other purpose of the invention is, there is provided a kind of film with field-effect mobility and high reliability high is brilliant Body pipe.
According to the present invention it is possible to provide following sputtering target etc..
1. a kind of sputtering target, it is by the oxygen containing phosphide element (In), tin element (Sn), Zn-ef ficiency (Zn) and aluminium element (Al) Compound is formed,
Containing with InAlO3(ZnO)mThe framework compound that (m be 0.1~10) is represented, the phosphide element, tin element, The atomic ratio of Zn-ef ficiency and aluminium element meets following formula (1)~(4).
0.10≤In/(In+Sn+Zn+Al)≤0.60 (1)
0.01≤Sn/(In+Sn+Zn+Al)≤0.30 (2)
0.10≤Zn/(In+Sn+Zn+Al)≤0.65 (3)
0.01≤Al/(In+Sn+Zn+Al)≤0.30 (4)
In formula, In, Sn, Zn and Al represent the material of phosphide element in sputtering target, tin element, Zn-ef ficiency and aluminium element respectively Amount.
2. the sputtering target according to described in 1, wherein, it is described with InAlO3(ZnO)mThe same tying that (m is 0.1~10) represents Structure compound is selected from InAlZn2O5The framework compound of expression and with InAlZnO4The framework compound of expression In more than a kind.
3. the sputtering target according to described in 1 or 2, it contains with Zn2SnO4The spinel structure compound of expression.
4., according to any one of 1~3 sputtering target recorded, it is not contained with In2O3The bixbyite structure chemical combination of expression Thing.
5., according to any one of 1~4 sputtering target recorded, its relative density is more than 98%.
6., according to any one of 1~5 sputtering target recorded, its body resistivity is below 5m Ω cm.
7. a kind of manufacture method of sputtering target, including by the oxide containing phosphide element, tin element, Zn-ef ficiency and aluminium element Formed body sintering temperature is warmed up to 0.1~2 DEG C/min of programming rate from 800 DEG C and 10 is kept under the sintering temperature ~50 hours and sinter operation, the sintering temperature is 1200 DEG C~1650 DEG C of scope.
8. a kind of oxide semiconductor thin-film, it uses the sputtering target of any one of 1~6 record, using sputtering film-forming Form.
9. a kind of manufacture method of oxide semiconductor thin-film, it is containing selected from hydrone, oxygen molecule and an oxidation two Under more than a kind atmosphere with the mixed gas of rare-gas atom in nitrogen molecular, any one of 1~6 sputtering recorded is used Target utilizes sputtering film-forming.
10. the manufacture method of the oxide semiconductor thin-film according to described in 9, wherein, the mixed gas are at least to contain There are the mixed gas of rare-gas atom and hydrone.
The manufacture method of 11. oxide semiconductor thin-film according to described in 10, wherein, it is contained in the mixed gas The ratio of hydrone is calculated as 0.1%~25% with intrinsic standoff ratio.
12. according to any one of 9~11 record oxide semiconductor thin-films manufacture method, wherein, to in vacuum Interior is separated by the facing position of the sputtering target of more than 3 of the spacing parallel arranging of regulation setting, substrate is transported successively, to institute State each target by AC power alternately apply negative potential and positive potential, output branch of at least one from AC power and with 2 with On target connection, the switching of the target for carrying out applying current potential between the target more than 2, at the same make on target generation plasma and Substrate surface film forming.
The manufacture method of 13. oxide semiconductor thin-film according to described in 12, wherein, by the exchange of the AC power Power density is set to 3W/cm2Above 20W/cm2Below.
The manufacture method of 14. oxide semiconductor thin-film according to described in 12 or 13, wherein, the frequency of the AC power Rate is 10kHz~1MHz.
A kind of 15. thin film transistor (TFT)s, it has using any one of 9~14 oxide semiconductors recorded as channel layer The oxide semiconductor thin-film of the manufacture method film forming of film.
16. thin film transistor (TFT) according to described in 15, wherein, field-effect mobility is 15cm2/ more than Vs.
A kind of 17. display devices, it possesses the thin film transistor (TFT) described in 15 or 16.
According to the present invention it is possible to provide a kind of high density and low-resistance sputtering target.
According to the present invention it is possible to provide the thin film transistor (TFT) with field-effect mobility and high reliability high.
Brief description of the drawings
Fig. 1 is the figure of the sputter equipment for representing used in an embodiment of the invention.
Fig. 2 is the figure of the X-ray diffractogram for representing the sintered body obtained in embodiment 1.
Specific embodiment
Hereinafter, sputtering target of the invention etc. is described in detail, but the present invention is not limited to following implementation methods And embodiment.
[sputtering target]
Sputtering target of the invention is by the oxygen containing phosphide element (In), tin element (Sn), Zn-ef ficiency (Zn) and aluminium element (Al) Compound is formed, containing with InAlO3(ZnO)mThe framework compound that (m is 0.1~10) represents.
Homology crystal structure be comprising by the crystal layer of different material overlap it is several layers of obtained by have it is macrocyclic " naturally super The crystal of lattice " structure.Crystal cycle or film layer thickness in the case of nanometer degree, framework compound can be with Show the intrinsic characteristics different from the property of single material or the mixed crystal for equably mixing.
Sputtering target of the invention is by containing with InAlO3(ZnO)mThe framework compound of expression, and target can be improved Relative density, target resistivity can be set to such as below 5m Ω cm.Because the resistivity of target is below 5m Ω cm, such that it is able to Suppress paradoxical discharge.
As the oxide crystal for obtaining homology crystal structure, can enumerate with RAO3(MO)mThe oxide crystal of expression. Herein, R is the metallic element of positive trivalent, for example, can enumerate In, Ga, Al, Fe, B.A is the metal unit of the positive trivalents different from R Element, for example, can enumerate Ga, Al, Fe.M is the metallic element of positive divalence, for example, can enumerate Zn, Mg.R, A and M both may be used respectively Being identical metallic element, or different metallic elements.In addition, m is, for example, integer, and preferably 0.1~10, it is more excellent Elect 0.5~7, more preferably 1~3 as.
Contained by target with InAlO3(ZnO)mThe framework compound of expression can be independent one kind or two or more mixing Compound, is preferably selected from InAlZn2O5The framework compound of expression and with InAlZnO4The framework compound of expression In more than a kind.
With InAlZn2O5The framework compound of expression and with InAlZnO4The framework compound of expression is all suitable It is that In, A are that Al, M are the situation of Zn in R.
Framework compound in target can be confirmed using X-ray diffraction, for example, can be obtained according to by crushing target The X-ray diffractogram that obtains of powder or directly determined by target and the homology phase envisioned based on ratio of components crystal structure X-ray Diffraction pattern unanimously confirms.Specifically, can according to by JCPDS (Joint Committee of Powder Diffraction Standards) the crystal structure X-ray diffractogram of homology phase that obtains of card unanimously confirms.
And, InAlZnO4Framework in X-ray diffraction, show the No.40-0258's of JCPDS databases Peak type or similar (being displaced) peak type.In addition, InAlZn2O5Framework show the No.40- of JCPDS databases 0259 peak type or similar (being displaced) peak type.
Sputtering target of the invention is preferably comprised with Zn2SnO4The spinel structure compound of expression.
So-called spinel structure, such as《Crystal chemistry》As disclosed in (talk society, the emerging work of middle zero diopter, 1973) etc., lead to Refer to AB2X4Type or A2BX4The structure of type, spinel structure compound is referred to as by the compound with this kind of crystal structure.
It is general that anion (usually oxygen) takes cubic closest packing in spinel structure, in its tetrahedral interstice and Cation is there are in a part for octahedral interstice.And, a part for atom, ion in crystal structure is by other former The intrusion type solid solution that substitutional solid solution that son has been replaced, other atoms are added into position between lattice is also contained in sharp crystalline substance In stone structure compound.
Sputtering target is by containing with Zn2SnO4The spinel structure compound of expression, and can suppress to constitute the oxide of target In crystal abnormal grain growth.The reason for abnormal grain growth is likely to become the paradoxical discharge in sputtering.
In for sputtering target with Zn2SnO4The presence or absence of spinel structure compound of expression, it is possible to use X-ray diffraction Confirm.
With Zn2SnO4The spinel structure compound of expression show the No.24-1470 of JCPDS databases peak type or Similar (being displaced) peak type.
Sputtering target of the invention is not preferably contained with In2O3The bixbyite structural compounds of expression.
So-called bixbyite structure (or crystal structure of rare-earth oxide c-type), also referred to as rare-earth oxide c-type Or Mn2O3(I) type oxide.Such as《The technology of nesa coating》(publication of (strain) OHM companies, JSPS, transparent oxygen The committee of compound photoelectron material the 166th compiles, 1999) etc. disclosed in as, stoichiometric proportion is M2X3(M is cation, X It is anion and usually oxonium ion), and 1 structure cell is by M2X3：(M is 32, X is 48 for 16 molecules, total 80 atom It is individual) constitute.
With In2O3The bixbyite structural compounds of expression also include using a part for the atom in crystal structure, ion The substitutional solid solution of other atomic substitutions, the intrusion type solid solution that other atoms are added to position between lattice.
In for sputtering target with In2O3The presence or absence of bixbyite structural compounds of expression, it is possible to use X-ray diffraction To confirm.
With In2O3The bixbyite structural compounds of expression show JCPDS (Joint Committee on Powder Diffraction Standards) database No.06-0416 peak type or similar (being displaced) peak type.
Constitute sputtering target of the invention, contain phosphide element (In), tin element (Sn), Zn-ef ficiency (Zn) and aluminium element (Al) Oxide meet following atomic ratios.Following atomic ratios are met by oxide, so that it may so that the relative density of target be 98% with Upper and body resistivity is below 5m Ω cm.
0.10≤In/(In+Sn+Zn+Al)≤0.60 (1)
0.01≤Sn/(In+Sn+Zn+Al)≤0.30 (2)
0.10≤Zn/(In+Sn+Zn+Al)≤0.65 (3)
0.01≤Al/(In+Sn+Zn+Al)≤0.30 (4)
In formula, In, Sn, Zn and Al represent the material of phosphide element in sputtering target, tin element, Zn-ef ficiency and aluminium element respectively Amount.
In formula (1), in the case where the atomic ratio of In elements is less than 0.10, the bulk resistance of sputtering target is uprised, it is possible to DC sputterings cannot be carried out.
On the other hand, in the case where the atomic ratio of In elements is more than 0.60, it is possible to generated with In in target2O3Represent Bixbyite structural compounds.In target in InAlZnO4Framework compound, InAlZn2O5Framework compound, Zn2SnO4Spinel structure compound beyond also contain In2O3Bixbyite structural compounds in the case of, due to every kind of The speed that crystalline phase is sputtered is different, therefore excavation can be produced to remain, it is possible to produce paradoxical discharge.In addition, sintering when In2O3Cohesion part there is abnormal grain growth, remaining pore, the overall density of sintered body is possible without improving.
For the foregoing reasons, formula (1) is 0.10≤In/ (In+Sn+Zn+Al)≤0.60, preferably 0.15≤In/ (In+ Sn+Zn+Al)≤0.50, more preferably 0.20≤In/ (In+Sn+Zn+Al)≤0.40.
In formula (2), in the case where the atomic ratio of tin element is less than 0.01, oxide density will not be improved fully, target Bulk resistance be possible to uprise.On the other hand, in the case where the atomic ratio of tin element is more than 0.30, the film obtained by target Dissolubility reduction in wet etchant, it is possible to so that Wet-type etching becomes difficult.
For the foregoing reasons, formula (2) is 0.01≤Sn/ (In+Sn+Zn+Al)≤0.30, preferably 0.05≤Sn/ (In+ Sn+Zn+Al)≤0.25, more preferably 0.07≤Sn/ (In+Sn+Zn+Al)≤0.18.
In formula (3), in the case where the atomic ratio of Zn-ef ficiency is less than 0.10, the film obtained by target has as amorphous film Potentially unstable.On the other hand, in the case where the atomic ratio of Zn-ef ficiency is more than 0.65, the film of gained is in wet etchant Dissolution velocity it is too high, it is possible to so that Wet-type etching becomes difficult.
For the foregoing reasons, formula (3) is 0.10≤Zn/ (In+Sn+Zn+Al)≤0.65, preferably 0.25≤Zn/ (In+ Sn+Zn+Al)≤0.60, more preferably 0.40≤Zn/ (In+Sn+Zn+Al)≤0.60.
In formula (4), in the case where the atomic ratio of aluminium element is less than 0.01, except target resistance is possible without fully dropping Beyond low, in the case of the channel layer for forming TFT using target, the reliability of TFT is it is also possible to deterioration.On the other hand, in aluminium In the case that the atomic ratio of element is more than 0.30, Al is generated in target2O3, it is possible to produce paradoxical discharge.
For the foregoing reasons, formula (4) is 0.01≤AI/ (In+Sn+Zn+Al)≤0.30, preferably 0.02≤Al/ (In+ Sn+Zn+Al)≤0.25, more preferably 0.02≤Al/ (In+Sn+Zn+Al)≤0.15.
The atomic ratio of contained each element can utilize inductively coupled plasma apparatus for analyzing luminosity (ICP-AES) in target Obtained to carrying out quantitative analysis containing element.
Specifically, it is vaporific when liquor sample is made of atomizer, import argon plasma (about 6000~8000 DEG C) When middle, the element in sample is absorbed by heat energy and is excited, and orbital electron moves to the track of high level from ground state.The track Electronics is 10-7~10-8Second moves left and right the track of more low-lying level.Now the difference of energy is radiated as light and is lighted. Because the light shows the intrinsic wavelength of element (spectrum line), therefore the presence of element can be confirmed according to the presence or absence of spectrum line (qualitative analysis).
Further, since the size (luminous intensity) of each spectrum line is proportional to the first prime number in sample, thus by with The titer of concentration known compares can be to obtain sample solution concentration (quantitative analysis).
After contained element is determined using qualitative analysis, content is obtained using quantitative analysis, can be with according to the result Obtain the atomic ratio of each element.
The oxide for constituting sputtering target can also contain In, Sn, Zn and Al in the scope for not damaging effect of the invention Inevitable impurity in addition, it is also possible to be substantially only made up of In, Sn, Zn and Al.
The preferred relative density of sputtering target of the invention is more than 98%.Particularly above carried in large substrate (more than 1G sizes) Sputtering power high and by the case of oxide semiconductor film forming, relative density is preferably more than 98%.
If relative density is more than 98%, the sputtering state of stabilization can be kept.Splashed being improved using large substrate Penetrate power and in the case of film forming, target surface melanism is possible to if relative density is less than 98% or paradoxical discharge is produced.Phase More than 98.5%, more preferably more than 99% are preferably to density.
The relative density of target can be determined using Archimedes method.Relative density is preferably less than 100%.It is being more than In the case of 100%, have and metallic is produced in sintered body or the situation of lower oxyde is generated, it is necessary to strictly adjust It is made into oxygen supply amount during film.
Alternatively, it is also possible to after sintering described later, carry out postprocessing working procedures such as the heat treatment operation under reducing atmosphere etc. To adjust density.Reducing atmosphere can use atmosphere or their mixed-gas atmospheres such as argon, nitrogen, hydrogen.
The body resistivity (electric conductivity) of target is preferably below 5m Ω cm, more preferably below 3m Ω cm.By making the body of target Resistivity is below 5m Ω cm, can suppress paradoxical discharge.
Above-mentioned body resistivity can be determined using resistivity meter based on four probe method.
The maximum particle diameter for constituting the crystal in the oxide of sputtering target is preferably less than 8 μm.If crystal growth is to being more than 8 μm of particle diameter, it is likely that the reason for as dross (nodule).
In the case of using sputtering cutting target surface, the speed that it is cut is different according to the direction of crystal face, in target Surface produces concavo-convex.The concavo-convex crystal particle diameter for being sized depending on being present in sintered body.It is believed that by with big In the target that the oxide of crystal particle diameter is formed, its concavo-convex change is big, and dross is produced from its convex portion.
For the maximum particle diameter of the crystal in sputtering target, sputtering target be shaped as circle in the case of, at round center At point (at 1) and the central point on 2 orthogonal center lines of the central point and total the 5 of the intermediate point (at 4) of peripheral part, In addition, sputtering target be shaped as quadrangle in the case of, the center (at 1) and on the diagonal of quadrangle at the center point Point adds up at 5 with the intermediate point (at 4) in corner, to the maximum particle assay observed in the inframe of 100 μm of square its most Major diameter, is represented with the average value of the particle diameter of the maximum particle for being respectively present in this inframe at 5.For particle diameter, to crystal grain Major diameter be measured.Crystal grain can be observed using scanning electron microscope (SEM).
[manufacture method of sputtering target]
The manufacture method of sputtering target of the invention for example includes 2 following operations.
(1) operation for mix starting compound, shaping and be made formed body
(2) operation for sintering above-mentioned formed body
Hereinafter, these operations are illustrated.
(1) operation for mix starting compound, shaping and be made formed body
Starting compound is not particularly limited, it is possible to use comprising more than a kind selected from the element in In, Sn, Zn and Al Compound, as long as the mixture of the starting compound for being used meets following atomic ratios.
0.10≤In/(In+Sn+Zn+Al)≤0.60 (1)
0.01≤Sn/(In+Sn+Zn+Al)≤0.30 (2)
0.10≤Zn/(In+Sn+Zn+Al)≤0.65 (3)
0.01≤Al/(In+Sn+Zn+Al)≤0.30 (4)
In formula, In, Sn, Zn and Al represent the amount of substance of phosphide element, tin element, Zn-ef ficiency and aluminium element respectively.
As the above-mentioned compound selected from the element in In, Sn, Zn and Al for including more than a kind, for example, can enumerate oxygen Change the combination of indium, tin oxide, zinc oxide and aluminum metal or the combination of indium oxide, tin oxide, zinc oxide and aluminum oxide etc..
And, above-mentioned raw materials compound is preferably powder.
Starting compound is preferably the mixed-powder of indium oxide, tin oxide, zinc oxide and aluminum oxide.
In the feed using in the case of elemental metals, for example, by indium oxide, tin oxide, zinc oxide and aluminum metal In the case that combination is used as material powder, there is the clipped wire of aluminium in the sintered body of gained, target table is had in film forming The situation that the clipped wire in face is melted and released not from target, the composition of the film of gained differs widely sometimes with the composition of sintered body.
In the case where starting compound is powder, the average grain diameter of the material powder is preferably 0.1 μm~1.2 μm, more Preferably 0.1 μm~1.0 μm.The average grain diameter of material powder can be determined using laser diffraction formula size distribution device etc..
For example, the In that average grain diameter is 0.1 μm~1.2 μm can will be contained2O3Powder, average grain diameter are 0.1 μm~1.2 μ The SnO of m2Powder, average grain diameter are 0.1 μm~1.2 μm of ZnO powder and Al that average grain diameter is 0.1 μm~1.2 μm2O3Powder Oxide as material powder, they are concocted with meeting the ratio of above-mentioned formula (1)~(4).
The mixing of starting compound, manufacturing process are not particularly limited, it is possible to use known method is carried out.For example, to In the material powder of the mixed powder containing the oxide comprising indium oxide powder, putty powder, zinc oxide and alumina powder, hydrous water Series solvent, after the slurries of gained are mixed more than 12 hours, carries out separation of solid and liquid drying-granulating, next, this is granulated Thing shapes in being put into die box, thus obtains formed body.
For mixing, it is possible to use ball mill, vibration mill, ball mill of wet type or dry type etc..It is uniform in order to obtain And fine crystal grain and emptying aperture, the crushing efficiency of most preferably short time and agglomerate is high, additive dispersity is also good Ball mill mixing method.
In the case where being mixed using ball mill, the incorporation time is preferably set to more than 15 hours, is more preferably set to 19 small When more than.Because, if incorporation time is not enough, it is likely that generate Al in the sintered body for finally giving2O3Deng high resistance Compound.
In the case where being pulverized and mixed using ball mill, the incorporation time is according to the size of device, the slurries amount for the treatment of And it is different, but the size distribution in slurries can be well suited to less than 1 μm in all homogeneous mode.
In addition, no matter in the case of which kind of mixed method, the adhesive of any amount is all preferably added in mixing, while Mixed.In adhesive, it is possible to use polyvinyl alcohol, vinyl acetate etc..
Using the granulation of the material powder slurries being mixed to get pelletizing is made preferably by rapidly drying-granulating.As with In the device for carrying out rapidly drying-granulating, spray dryer is widely used.Specific drying condition will be according to wanting dry Many conditions such as hot blast temperature, air quantity used are determined in concentration of slurry, the drying of slurries, therefore are needed when implementing advance Obtain optimum condition.
On the other hand, if granulated using spontaneously drying, because sinking speed is according to the proportion of material powder Difference and it is different, therefore In can be produced2O3Powder, SnO2Powder, ZnO powder and Al2O3The separation of powder, it is possible to cannot obtain Even pelletizing.If making sintered body using the uneven pelletizing, can there is Al inside sintered body2O3Deng having into The situation of the reason for for paradoxical discharge in sputtering.
To the pelletizing of gained, generally can for example apply by using metal moulding press or cold isostatic press (CIP) 1.2ton/cm2More than pressure be made formed body.
(2) operation for sintering formed body
Sintering temperature by the molding of gained at 1200~1650 DEG C is sintered 10~50 hours, it is possible to sintered Body.
Above-mentioned sintering temperature is preferably 1350~1600 DEG C, more preferably 1400~1600 DEG C, more preferably 1450 ~1600 DEG C.In addition, above-mentioned sintering time is preferably 12~40 hours, more preferably 13~30 hours.
If sintering temperature is less than 1200 DEG C or sintering time is less than 10 hours, Al can be internally formed in target2O3Deng having The reason for being likely to become paradoxical discharge.On the other hand, if firing temperature is more than 1650 DEG C or firing time is more than 50 hours, The increase of average crystal particle diameter or the generation of thick emptying aperture then can be caused because of significant grain growth, it is possible to as sintering The reason for reduction, paradoxical discharge of body intensity.
As sintering method used in the present invention, in addition to normal pressure-sintered method, can also be added using drop stamping, oxygen The pressure sintering method such as pressure, high temperature insostatic pressing (HIP).But, reduction, a large amount of manufacturing feasibilities from manufacturing cost, can be easily manufactured From the viewpoint of large-scale sintered body, it is preferred to use normal pressure-sintered method.
In normal pressure-sintered method, formed body is sintered in air atmosphere or oxidizing gas atmosphere, preferably in oxidizing gas gas Sintered in atmosphere.So-called oxidizing gas atmosphere, preferably oxygen atmosphere.The preferred oxygen concentration of oxygen atmosphere is, for example, 10~100 bodies The atmosphere of product %.In the manufacture method of above-mentioned sintered body, by importing oxygen atmosphere in temperature-rise period, can further carry Sintered density high.
Programming rate during sintering is preferably set to from 800 DEG C to 0.1~2 DEG C/min of sintering temperature (1200~1650 DEG C).
In the sputtering target of the oxide containing phosphide element (In), tin element (Sn), Zn-ef ficiency (Zn) and aluminium element (Al), 800 DEG C~its more than temperature range be to sinter most violent scope.If the programming rate in the temperature range is less than 0.1 DEG C/min, then grain growth becomes notable, it is possible to cannot realize densification.On the other hand, if programming rate is more than 2 DEG C/min, it is likely that Al is separated out inside target2O3Deng.
The programming rate of sintering temperature is preferably 0.1~1.3 DEG C/min from 800 DEG C, more preferably 0.1~1.1 DEG C/ Minute.
In order that the body resistivity of the sintered body obtained in above-mentioned firing process is homogenized in whole target, it is also possible to according to Need to set reduction operation.
As restoring method, for example, can enumerate method by reducibility gas, by vacuum firing or inert gas Reduction etc..
In the case of the reduction treatment by reducibility gas, it is possible to use hydrogen, methane, carbon monoxide or these gas Mixed gas of body and oxygen etc..In addition, in the case of the reduction treatment burnt till in by inert gas, it is possible to use nitrogen, Mixed gas of argon or these gases and oxygen etc..
Temperature during reduction treatment is usually 100~800 DEG C, preferably 200~800 DEG C.In addition, the time of reduction treatment Usually 0.01~10 hour, preferably 0.05~5 hour.
If summarized to more than, the manufacture method of sintered body used is for example to containing indium oxide in the present invention Coordinate water solvent in the material powder of the mixed powder of powder, putty powder, oxide powder and zinc and alumina powder and by the slurries of gained After mixing more than 12 hours, separation of solid and liquid drying-granulating is carried out, next, shaped during the granules are added into die box, Thereafter, by the molding of gained in oxygen atmosphere, with 0.1~2 DEG C/min from 800 DEG C to the programming rate of sintering temperature, 1200~1650 DEG C are burnt till 10~50 hours, thus can be obtained by sintered body.
The sintered body obtained by processing and utilization aforesaid operations, it is possible to be made sputtering target of the invention.Specifically, lead to Cross by sintered body machining for the shape being adapted to be mounted in sputter equipment is made sputtering target raw material, by the way that the target is former Material is bonded on backboard, can be made sputtering target.
When sintered body is made into target raw material, being for example made surface roughness Ra with surface grinding machine grinding and sintering body is Less than 0.5 μm of raw material.Herein, it is also possible to which the sputter face also to target raw material implements mirror finish, by average surface roughness Degree Ra is set to less than 1000 angstroms.
Mirror finish (grinding) can (mechanical lapping and chemistry grind using mechanical lapping, chemical grinding, mechanical-chemistry grinding Mill be used in combination) etc. known grinding technique.For example, can be by with bonded-abrasive polishing machine (polishing fluid：Water) it is polished to # More than 2000 or with free abrasive disk (grinding-material：SiC paste etc.) polishing after, change grinding-material into diamond paste and enter Row is polished and obtained.It is not particularly limited for this kind of Ginding process.
The surface of preferred pair target raw material is finished using the skive of 200~10, No. 000, particularly preferably Finished using the skive of 400~No. 5,000.If using the Buddha's warrior attendant less than No. 200 or more than No. 10,000 Stone sand wheel, then target raw material be possible to be easily broken.
The surface roughness Ra of target raw material is preferably provided with to be less than 0.5 μm, do not have directive abradant surface.If Ra is big There is directionality in 0.5 μm or in abradant surface, it is likely that cause paradoxical discharge or produce particle.
Finally, the target raw material to gained carry out cleaning treatment.Can be cleaned using air blast or flowing water in cleaning treatment etc.. When foreign matter is removed using air blast, if carrying out air-breathing with dust catcher from the opposite side of nozzle, can more effectively remove.
And, the limit is there are in air blast, the flowing water cleaning more than, therefore can also also carry out ultrasonic wave cleaning etc.. It is effective method that multiple carry out ultrasonic wave cleaning method with exciting is allowed between 25~300KHz of frequency.For example it is preferred Excite 12 kinds of frequencies and carry out ultrasonic wave cleaning every 25KHz ground is multiple between 25~300KHz of frequency.
The thickness of target raw material is usually 2~20mm, particularly preferably preferably 3~12mm, 4~6mm.
It is bonded on backboard by the target raw material that will be obtained as described above, it is possible to obtain sputtering target.In addition, also may be used It is installed on 1 backboard with by multiple target raw material, is substantially made 1 target.
Sputtering target of the invention can make relative density be more than 98% and body resistivity using above-mentioned manufacture method It is below 5m Ω cm, in sputtering, the generation of paradoxical discharge can be suppressed.In addition, sputtering target of the invention can be effective, honest and clean The oxide semiconductor thin-film of valency and energy-conservation ground formation high-quality.
[oxide semiconductor thin-film]
Sputtering film-forming is utilized by using sputtering target of the invention, oxide semiconductor of the invention can be obtained thin Film.
Oxide semiconductor thin-film of the invention is formed by indium, tin, zinc, aluminium, oxygen, preferably meet following atomic ratios (1)~ (4)。
0.10≤In/(In+Sn+Zn+Al)≤0.60 (1)
0.01≤Sn/(In+Sn+Zn+Al)≤0.30 (2)
0.10≤Zn/(In+Sn+Zn+Al)≤0.65 (3)
0.01≤Al/(In+Sn+Zn+Al)≤0.30 (4)
In formula, In, Sn, Zn and Al represent phosphide element in oxide semiconductor thin-film, tin element, Zn-ef ficiency and aluminium respectively The amount of substance of element.
In formula (1), if the amount of In elements is less than 0.10, the bulk resistance of sputtering target is uprised, therefore cannot carry out DC Sputtering.On the other hand, if the amount of In elements is more than 0.60, the reliability when the film of formation is applied in the channel layer of TFT Property be possible to deterioration.
In formula (2), if the amount of Sn elements is less than 0.01, target resistance is raised, therefore is produced in spatter film forming abnormal Electric discharge, film forming is possible without stabilizing.On the other hand, if the amount of Sn elements is more than 0.30, the film of gained is in wet type Dissolubility reduction in etchant, therefore Wet-type etching becomes difficult.
In formula (3), if the amount of Zn elements is less than 0.10, the film of gained is possible to unstable as amorphous film.Separately On the one hand, if the amount of Zn elements is more than 0.65, the dissolution velocity of the film in wet etchant of gained is too high therefore wet Formula etching becomes difficult.
In formula (4), if the amount of Al elements is less than 0.01, partial pressure of oxygen during film forming is possible to raise.Due to Al elements And the combination of oxygen is strong, therefore partial pressure of oxygen when can reduce film forming.In addition, the situation in formation channel layer is applied to TFT Lower reliability is possible to deterioration.On the other hand, if the amount of Al elements is more than 0.30, Al can be generated in target2O3, in sputtering Paradoxical discharge is produced during film forming, film forming is possible to destabilization.
The carrier concentration of oxide semiconductor thin-film is usually 1019/cm3Hereinafter, preferably 1013~1018/cm3, enter one Step is preferably 1014~1018/cm3, particularly preferably 1015~1018/cm3。
If the carrier concentration of oxide skin(coating) is more than 1019cm-3, then when the elements such as thin film transistor (TFT) are constituted, it is possible to Produce leakage current.Further, since be changed into normally opened or on-off ratios diminishing, thus it is possible to that good transistor cannot be played Energy.If additionally, carrier concentration is less than 1013cm-3, then carrier number is few, is driven it is therefore possible to cannot function as TFT.
The carrier concentration of oxide semiconductor thin-film can be measured using Hall effect assay method.
Sputtering target of the invention can apply the fireballing DC sputtering methods of film forming due to high conductivity.
In addition to above-mentioned DC sputtering methods, RF sputtering methods, AC sputtering methods, pulse DC sputtering methods, Ke Yijin can also be applied Sputtering of the row without paradoxical discharge.
Oxide semiconductor thin-film can also be swashed using above-mentioned sintered body using vapour deposition method, sputtering method, ion plating method, pulse Light vapour deposition method etc. makes.
As sputter gas (atmosphere), it is possible to use the mixed gas of the rare-gas atom such as argon and oxidizing gas.Institute Meaning oxidizing gas, can enumerate O2、CO2、O3、H2O、N2O etc..Sputter gas preferably comprise rare-gas atom and selected from moisture The mixed gas of the molecule of one or more of son, oxygen molecule and nitrous oxide molecules, it is more preferably former containing rare gas The mixed gas of son and at least hydrone.
Partial pressure of oxygen ratio during spatter film forming is preferably set to 0% less than 40%.In partial pressure of oxygen than being more than 40% Under the conditions of the carrier concentration of film that makes be greatly lowered, carrier concentration is likely to be less than 1013cm-3。
Partial pressure of oxygen ratio preferably 0%~30%, particularly preferably 0%~20%.
The intrinsic standoff ratio of contained hydrone in sputter gas (atmosphere) when sull of the invention is piled up, [H2O]/([H2O]+[rare gas]+[other molecules]) it is preferably 0.1~25%.
In addition, if the intrinsic standoff ratio of water is more than 25%, then the reduction of film density is notable, therefore the overlap of the 5s tracks of In becomes It is small, it is possible to cause the reduction of mobility.The intrinsic standoff ratio of the water in atmosphere during sputtering is more preferably 0.7~13%, especially excellent Elect 1~6% as.
Substrate temperature when carrying out film forming using sputtering is preferably 25~120 DEG C, more preferably 25~100 DEG C, especially excellent Elect 25~90 DEG C as.If substrate temperature during film forming is higher than 120 DEG C, oxygen imported during film forming etc. receives reductions, heats The carrier concentration of film afterwards is possible to more than 1019/cm3.In addition, if substrate temperature during film forming is less than 25 DEG C, then it is thin The film density reduction of film, the mobility of TFT is likely to decrease.
It is preferred that the sull obtained using sputtering being kept for 15 minutes~5 hours at 150~500 DEG C again and implementing to move back Fire treatment.Annealing temperature after film forming is more preferably more than 200 DEG C and less than 450 DEG C, more preferably more than 250 DEG C And less than 350 DEG C.By implementing above-mentioned annealing, characteristic of semiconductor can be obtained.
In addition, atmosphere during heating should be not particularly limited, but from from the viewpoint of carrier controlling, preferably greatly Gas atmosphere, oxygen circulation atmosphere.
In the post processing annealing operation of sull, can under the existence of oxygen or in the absence of state under use Lamp annealing device, laser anneal device, heat plasma body device, hot air heating apparatus, contact heater etc..
The distance between target and substrate during sputtering are 1~15cm preferably in the film forming face vertical direction with substrate, are entered One step is preferably 2~8cm.In the case where the distance is less than 1cm, the kinetic energy for reaching the particle of the target constitution element of substrate becomes Greatly, it is not only the possibility to that good membrane property cannot be obtained, and is possible to be distributed in the face of generation thickness and electrical characteristics.The opposing party Face, in the case where the interval of target and substrate is more than 15cm, the kinetic energy for reaching the particle of the target constitution element of substrate is too small, it is impossible to Obtain fine and close film, it is possible to good characteristic of semiconductor cannot be obtained.
The film forming of sull is sputtered preferably under the atmosphere that magnetic field intensity is 300~1500 Gausses.In magnetic field intensity In the case of less than 300 Gausses, due to plasma density step-down, therefore nothing is possible in the case of high-resistance sputtering target Method is sputtered.On the other hand, in the case of more than 1500 Gausses, the controlling of the electrical characteristics in thickness and film is possible to be deteriorated.
The pressure (sputtering pressure) of gas atmosphere as long as the scope that can stably discharge of plasma, just without special Limit, but preferably 0.1~3.0Pa, more preferably 0.1~1.5Pa, particularly preferably 0.1~1.0Pa.In sputtering More than in the case of 3.0Pa, the mean free path of sputtering particle shortens pressure, and the density of film is likely to decrease.In addition, splashing Injection pressure is possible to generate crystallite in film less than in the case of 0.1Pa in film forming.And, so-called sputtering pressure is to instruct Enter the gross pressure in the system when sputtering after the rare-gas atoms such as argon, hydrone, oxygen molecule etc. starts.
In order to remove the metallic pollutions such as the Cu of semiconductor substrate during manufacture thin film transistor (TFT), and in order to reduce The surface energy level that dangling bonds by gate insulating film surface etc. causes, preferably carries out semiconductor substrate, the cleaning on gate insulating film surface.
As cleaning solution, it is possible to use the solution containing cyano group (CN).It is used in cleaning to contain the molten of cyano group (CN) Liquid is adapted to use the solution for obtaining as follows, i.e. hydrogen cyanide (HCN) is dissolved in into pure water or ultra-pure water or selected from alcohol series solvent, ketone Series solvent, nitrile series solvent, aromatic hydrocarbon series solvent, carbon tetrachloride, ether series solvent, aliphatic chain alkane series solvent and they In at least a kind solvent in mixed solvent, then normal concentration is diluted to, and it is with ammonia spirit etc. that the hydrogen ion in solution is dense Degree index, so-called pH value are preferably adjusted to 9~14 scope.
Cyano group (CN) content is, for example, below 100ppm, and preferably 1ppm~10ppm preferably heats hydrogen ionexponent (pH) be 9~14 the solution containing cyano group, below 50 DEG C, be preferably 30 DEG C~40 DEG C scope set point of temperature, carry out Semiconductor substrate, the cleaning treatment on gate insulating film surface.
By using the HCN aqueous solution, cyanide ion (CN-) will react to form [Cu with the copper on substrate surface (CN)2]-And remove the copper that depollutes.[Cu(CN)2]-With the CN in the HCN aqueous solution-Ionic reaction, as [Cu (CN) under pH104]3- Stably exist.CN-The complex ion of ion is formed can be very big, even the HCN aqueous solution of extremely low concentration, CN-Ion can also have React and remove the copper that depollutes in effect ground.
Alternatively, it is also possible to carry out the film forming of oxide semiconductor thin-film using exchange sputtering as follows.
To the position facing with the target of be separated by the setting of the spacing parallel arranging of regulation in vacuum chamber more than 3, remove successively Send substrate, negative potential and positive potential alternately applied to each target from AC power, make on target produce plasma and in substrate table Film forming on face.
Now, between the target of more than 2 that at least one is connected from the output branch of AC power, carrying out Carried out while the switching of the target for applying current potential.That is, by output branch of at least one from above-mentioned AC power with 2 with On target connection, carry out film forming while different current potentials are applied to adjacent target.
And, using exchanging in the case that sputtering forms oxide semiconductor thin-film, it is also preferred that for example containing rare Gas atom and selected from one or more of hydrone, oxygen molecule and nitrous oxide molecules molecule mixed gas gas Sputtered under atmosphere, particularly preferably sputtered under the atmosphere of the mixed gas containing hydrone.
In the case of using AC spatter film formings, the excellent oxide skin(coating) of large-area uniformity can be industrially obtained, And it is expected to improve the utilization ratio of target.
In addition, in the case of spatter film forming on large-area substrates of 1 side more than 1m, such as preferably using as Japanese Unexamined Patent Publication The AC sputter equipments of the large area production as the record of 2005-290550 publications.
The AC sputter equipments that Japanese Unexamined Patent Publication 2005-290550 publications are recorded specifically have：Vacuum tank, be configured at it is true Substrate fixture inside dead slot and it is configured at the sputtering source of the position facing with the substrate fixture.AC sputterings are represented in Fig. 1 The major part of the sputtering source of device.Sputtering source has multiple sputtering portions, respectively the target 31a~31f with tabular, if with each The face being sputtered of target 31a~31f is configured as sputter face in identical plane as sputter face, then each sputtering portion.Respectively Target 31a~31f is formed as the elongated shape with length direction, and each target is same shape, the edge of the length direction of sputter face Partly (side) is separated by predetermined distance ground and is abreast configured.Thus, the side of adjacent target 31a~31f is parallel.
In the outside of vacuum tank, be configured with AC power 17a~17c, two terminals of each AC power 17a~17c it In a terminal and the electrode connection among two adjacent electrodes, another terminal is connected with another electrode.Respectively 2 terminals of AC power 17a~17c export the voltage of positive and negative opposed polarity, and target 31a~31f is closely pacified with electrode Dress, therefore 2 adjacent target 31a~31f are applied with the alternating voltage of mutually different polarity by AC power 17a~17c.Cause And, one among target 31a~31f adjacent to each other when being placed in positive potential, another is at being placed in the shape of negative potential State.
Magnetic field formation mechanism 40a~40f is configured with electrode and the face of target 31a~31f opposition sides.Each magnetic field forms machine Structure 40a~40f has the elongated annular magnet of the periphery size roughly equal with the periphery of target 31a~31f and compares ring respectively The short bar-shaped magnet of the length of shape magnet.
Each annular magnet is put down in the dead astern position of corresponding 1 target 31a~31f by the length direction with target 31a~31f Configure capablely.As noted previously, as target 31a~31f is separated by predetermined distance ground configured in parallel, therefore annular magnet is also separated by Configured with target 31a~31f identicals compartment of terrain.
In AC sputterings, AC power density during using oxide target is preferably 3W/cm2Above, 20W/cm2Below.In work( Rate density is less than 3W/cm2In the case of, film forming speed is slow, not economical enough in production.If greater than 20W/cm2, then target be possible to It is damaged.Preferred power density is 3W/cm2~15W/cm2。
The frequency of AC sputterings is preferably the scope of 10kHz~1MHz.If in below 10kHz, asking for noise can be produced Topic.If greater than 1MHz, then because plasma is wide, therefore can be sputtered beyond required target position, so as to have The situation that uniformity suffers damage.The frequency of preferred AC sputterings is 20kHz~500kHz.
As long as condition during sputtering other than the above etc. is properly selected from above-mentioned content.
[thin film transistor (TFT) and display device]
Above-mentioned sull can be used in thin film transistor (TFT), is particularly adapted as channel layer and uses, will The field-effect mobility of the thin film transistor (TFT) that oxide semiconductor thin-film of the invention is used in channel layer can show 15cm2The high mobility of/more than Vs, and high reliability can be shown.
As long as thin film transistor (TFT) of the invention has above-mentioned sull as channel layer, then its element is constructed without It is particularly limited to, can be constituted using known various elements.
The thickness of the channel layer of thin film transistor (TFT) of the invention is usually 10~300nm, preferably 20~250nm, more excellent Elect 30~200nm, particularly preferably more preferably 35~120nm, 40~80nm as.10nm is less than in the thickness of channel layer In the case of, the inhomogeneities of thickness during due to large area film forming, the characteristic of made TFT is possible to become not in face Uniformly.On the other hand, in the case where thickness is more than 300nm, film formation time is elongated, is industrially possible to use.
The channel layer of thin film transistor (TFT) of the invention can also after the annealing process at least in the region with gate electrode In partly crystallize.And, so-called crystallization refers to nucleus to be generated from the state of amorphous or from the state for generating nucleus Play growth crystal grain.It is resistance to for plasma process (CVD processing etc.) particularly when the part crystallization of back channel side is made Reproducibility is improved, and the reliability of TFT improves.
The region for having crystallized for example can be by transmission electron microscope (TEM：Transmission Electron Microscope electron beam diffraction picture) confirms.
The channel layer of thin film transistor (TFT) of the invention is generally used in N-type region domain, but can partly be led with p-type Si systems The various P-type semiconductors such as body, p-type oxide semiconductor, p-type organic semiconductor are combined and are used for PN junction transistor npn npn etc. various half In conductor device.
Thin film transistor (TFT) of the invention preferably possesses diaphragm on above-mentioned channel layer.The guarantor of thin film transistor (TFT) of the invention Cuticula preferably at least contains SiNx。SiNxWith SiO2Compared to the film that can form densification, therefore the degradation inhibiting effect with TFT Advantage high.
Diaphragm is in SiNxOutside, can also for example contain SiO2、Al2O3、Ta2O5、TiO2、MgO、ZrO2、CeO2、K2O、 Li2O、Na2O、Rb2O、Sc2O3、Y2O3、HfO2、CaHfO3、PbTiO3、BaTa2O6、Sm2O3、SrTiO3Or the oxide such as AlN etc..
Sull containing phosphide element (In), tin element (Sn), Zn-ef ficiency (Zn) and aluminium element (Al) of the invention Due to containing Al, therefore the reducing resistance processed by CVD is improved, it is difficult to by make the operation of diaphragm and by back channel side Reduction, can use SiN as diaphragmx。
It is preferred that before diaphragm is formed, ozone treatment, oxygen plasma treatment, nitrogen dioxide plasma are implemented to channel layer Body treatment or nitrous oxide corona treatment.As long as this kind for the treatment of is after formation channel layer, before diaphragm is formed, then No matter which at moment carry out can, but preferably not long ago carried out forming diaphragm.By carrying out this kind of pre-treatment, can To suppress the generation of the oxygen defect in channel layer.
In addition, if the hydrogen diffusion in oxide semiconductor film in TFT drivings, will cause the drift of threshold voltage, The reliability of TFT is likely to decrease.Processed by implementing to channel layer ozone, oxygen plasma treatment or nitrous oxide etc. from Daughter is processed, it is possible to stabilize the key of In-OH in membrane structure, suppresses the diffusion of the hydrogen in oxide semiconductor film.
And, in the photo-mask process of present embodiment, it is also possible to before painting erosion resistant agent, in oxide semiconductor film Surface forms the dielectric film that thickness is several nm or so.Oxide semiconductor film can be avoided directly to be connect with resist using the operation Touch, in can preventing contained impurity in resist from invading oxide semiconductor film.
Thin film transistor (TFT) is generally configured with substrate, grid, gate insulation layer, organic semiconductor layer (channel layer), source electrode and drain electrode. For channel layer known material can be used as described previously for substrate.
For forming the material of the gate insulating film in thin film transistor (TFT) of the invention it is not also specifically limited, can be arbitrarily The general material used of selection.Specifically, SiO can for example be used2、SiNx、Al2O3、Ta2O5、TiO2、MgO、ZrO2、 CeO2、K2O、Li2O、Na2O、Rb2O、Sc2O3、Y2O3、HfO2、CaHfO3、PbTiO3、BaTa2O6、SrTiO3、Sm2O3, AlN etc. changes Compound.In the middle of them, preferably SiO2、SiNx、Al2O3、Y2O3、HfO2、CaHfO3, more preferably SiO2、SiNx、HfO2、 Al2O3。
Gate insulating film can for example utilize plasma CVD (Chemical Vapor Deposition：Chemical gaseous phase is given birth to It is long) method formed.
In the case where forming gate insulating film using plasma CVD method, being formed on channel layer, in gate insulating film Hydrogen is spread in channel layer, it is possible to which the film quality for causing channel layer is reduced, the reliability of TFT is reduced.In order to prevent channel layer Film quality reduction, the reliability reduction of TFT, implement ozone treatment, oxygen plasma preferably before channel layer is formed to gate insulating film Treatment, nitrogen dioxide corona treatment or nitrous oxide corona treatment.By carrying out this kind of pre-treatment, can prevent The reduction of the film quality of channel layer, the reliability reduction of TFT.
And, the oxygen number of above-mentioned oxide is not necessarily consistent with stoichiometric proportion, for example, either SiO2Or SiOx Can.
Gate insulating film can also be the structure of more than 2 layers will be made up of different materials of dielectric film stacking.In addition, grid are exhausted Velum can be any one of crystal, polycrystalline, amorphous, but the polycrystalline or amorphous of preferably industrial easy to manufacture.
Material for forming each electrode of drain electrode, source electrode and grid in thin film transistor (TFT) of the invention is not limited especially System, can arbitrarily select general material used.ITO, IZO, ZnO, SnO can for example be used2Etc. transparency electrode, Al, Ag, The metal electrode of the metal electrodes such as Cu, Cr, Ni, Mo, Au, Ti, Ta or the alloy containing them.
S values can make the curve map of Log (Id)-Vg according to the result of transmission characteristic, and the inverse according to its slope is derived. The unit of S values is V/decade, preferably small value.S values are preferably below 0.8V/dec, more preferably below 0.5V/dec, More preferably below 0.3V/dec, particularly preferably below 0.2V/dec.If below 0.8V/dec, then driving voltage Diminish, it may be possible to reduce power consumption.Particularly, in the case of use in organic el display, when for DC driven When S values are set into below 0.3V/dec, it is possible to power consumption is greatly reduced, therefore preferably.
And, so-called S values (SwingFactor) refer to following value, i.e. when gate voltage is increased by off-state, by To on-state, leakage current sharp rises off-state, is the value for representing the dramatic degree.As shown in using following formula definition, will The incrementss of gate voltage when leakage current rises 1 order of magnitude (10 times) are set to S values.
S values=dVg/dlog (Ids)
S values are smaller, then sharp rise (《Thin-film transistor technologies it is blanket》, Ti raise great work, 2007 annuals, Census of manufacturing meeting).If S values are big, need to apply gate voltage high when connecting and being switched to disconnection, power consumption is possible to become big.
The sull formed by In, Sn, Zn, Al suitable for channel layer can utilize organic acid system etching solution (example Such as oxalic acid etching solution) carry out Wet-type etching, and be insoluble in inorganic acid system Wet-type etching liquid (such as phosphoric acid/nitric acid/acetic acid it is mixed Sour Wet-type etching liquid：PAN in), the selection with the Wet-type etching of the Mo (molybdenum), the Al (aluminium) that use in electrode etc. is than big.Thus, lead to Crossing the sull that will be formed by In, Sn, Zn, Al is used in channel layer, can make the thin film transistor (TFT) of channel etch type.
Each electrode of drain electrode, source electrode and grid can also be set to the multilayer knot of the conductive layer of be laminated different more than 2 layers Structure.Particularly source-drain electrode due to the requirement connected up to low resistance it is high, therefore the excellent metal of close property such as Ti, Mo can also be used The good conductors such as Al, Cu are clipped in the middle and are used.
Thin film transistor (TFT) of the invention can be applicable to FET, logic circuit, storage circuit, differential put In the various integrated circuits such as big circuit.Additionally, beyond scene effect transistor npn npn, electrostatic induction crystal can also be applied to In pipe, Schottky barrier transistor npn npn, Schottky diode, resistive element.
The composition of thin film transistor (TFT) of the invention can without limitation use bottom gate, bottom contact, top contact etc. known Constitute.
Particularly bottom gate is constituted and can obtain high-performance compared with amorphous silicon, the thin film transistor (TFT) of ZnO, therefore favorably. Bottom gate constitutes mask sheet number when easily cutting down manufacture, is easily reduced the manufacturing cost of the purposes such as giant display, therefore preferably.
Thin film transistor (TFT) of the invention goes in display device.
Used as the display of large area, the thin film transistor (TFT) of the bottom gate composition of particularly preferred channel etch type.Raceway groove loses Quarter type bottom gate constitute thin film transistor (TFT) photo-mask process when photomask number it is few, can at low cost manufacture display Use panel.Wherein, the thin film transistor (TFT) that the bottom gate of channel etch type is constituted and top contact is constituted is because the characteristics such as mobility are good And it is easy to industrialization, therefore particularly preferably.
Embodiment
Embodiment 1-8
[manufacture of oxidate sintered body]
Following oxide powders have been used as material powder.In being used as the average grain diameter of following oxide powders Value diameter D50, the average grain diameter is surveyed using laser diffraction formula particle size distribution device SALD-300V (Shimadzu Seisakusho Ltd.'s system) It is fixed.
Above-mentioned powder is weighed in the way of to reach the atomic ratio shown in table 1, equably after Crushing of Ultrafine mixing, shaping is added Granulated with adhesive.Then, in the raw material mixed powder being filled uniformly with into metal pattern, with cold press with the punching press of 140MPa Pressure press molding.
By so obtained formed body with the programming rate (from 800 DEG C to sintering temperature) shown in table 1, sintering temperature and burning The knot time sinters in sintering furnace and manufactures sintered body.Rise middle benefit gas and be set to oxygen atmosphere, other are set in air (atmosphere), cooling speed Degree is set to 15 DEG C/min.
[analysis of sintered body]
The relative density of the sintered body of gained is determined using Archimedes method.Confirm the phase of the sintered body of embodiment 1~8 It is more than 98% to density.
In addition, being surveyed based on four probe method (JIS R 1637) using resistivity meter (Mitsubishi Chemical's (strain) system, Lorester) Make the body resistivity (electric conductivity) of the sintered body of gained.The results are shown in Table 1.The burning of embodiment 1~8 as shown in table 1 The body resistivity of knot body is below 5m Ω cm.
Sintered body to gained carries out ICP-AES analyses, confirms as the atomic ratio shown in table 1.
In addition, have studied crystal structure using X-ray diffraction measure device (XRD) to the sintered body of gained.By embodiment 1 In the X-ray diffractogram of sintered body that obtains be shown in Fig. 2.
Analyzed pattern as a result, observing InAlZn in the sintered body of embodiment 12O5Framework and Zn2SnO4 Spinel structure.Crystal structure can utilize JCPDS (Joint Committee of Powder Diffraction Standards) card confirms.
According to the result of XRD, InAlZn is also observed for embodiment 2-82O5And/or InAlZnO4Framework and Zn2SnO4Spinel structure.InAlZn2O5Framework be JCPDS cards No.40-0259, Zn2SnO4Spinelle knot Structure is JCPDS cards No.24-1470.In embodiment 2, except observing InAlZn2O5And Zn2SnO4In addition, also observe InAlZnO4。InAlZnO4Framework be JCPDS cards No.40-0258.
In the sintered body of embodiment 1-8, In the reason for as paradoxical discharge is not observed2O3。
The condition determination of XRD is as follows.
Device：(strain) Rigaku Ultima-III
X-ray：Cu-K α line (wavelengthUsing graphite monochromator monochromatization)
2 θ-θ bounce techniques, continuous scanning (1.0 °/minute)
Sampling interval：0.02°
Slit DS, SS：2/3°、RS：0.6mm
To the sintered body of embodiment 1-8, the sintered body that utilization electron beam differential analyzer (EPMA) measure is obtained is have studied The dispersion of Sn, Al, as a result, not observing the aggregate of more than 8 μm of Sn or Al.Understand the sintered body of embodiment 1~8 Dispersiveness, uniformity it is extremely excellent.
The condition determination of EPMA is as follows.
Device name：JXA-8200 (Jeol Ltd.)
Accelerating potential：15kV
Irradiation electric current：50nA
Irradiation time (every 1 point)：50mS
[manufacture of sputtering target]
The surface of the sintered body obtained in embodiment 1~8 is ground with surface grinding machine, side, patch are cut off with diamond segment Close on backboard, the sputtering target of 4 inches of diameter is produced respectively.In addition, for embodiment 1,4,6, respectively with AC spatter film formings Purposes produces 200mm wide, 1700mm long, 6 targets of thickness 10mm.
[whetheing there is the confirmation of paradoxical discharge]
The sputtering target of 4 inches of the diameter of gained is installed in DC sputter equipments, uses in argon gas to divide as atmosphere Pressure ratio meter with the addition of 2% H2The mixed gas of O gases, 0.4Pa is set to by sputtering pressure, and substrate temperature is set into room temperature, is utilized The DC power of 400W, has carried out 10kWh and has continuously sputtered.Variation in voltage in sputtering is stored in data logger, it is thus identified that The presence or absence of paradoxical discharge.The results are shown in Table 1.
And, the presence or absence of above-mentioned paradoxical discharge is paradoxical discharge to be detected by monitoring voltage variation and is carried out.It is specific and Speech, the variation in voltage by the generation in the minute of 5 minutes is the situation of more than 10% of the rated voltage during sputtering is operated It is set to paradoxical discharge.Rated voltage particularly in operating is sputtered changed in the case of ± 10% in 0.1 second, produced conduct The differential of the arc of the paradoxical discharge of sputtering discharge, the stock utilization reduction of element, it is possible to be unsuitable for a large amount of productionizations.
[whetheing there is the confirmation of dross generation]
The sputtering target of 4 inches of diameter obtained by use, is used as atmosphere and with the addition of 3% in terms of intrinsic standoff ratio in argon gas The mixed gas of hydrogen, continuous 40 hours are sputtered, it is thus identified that the presence or absence of generation of dross.As a result, in embodiment In the sputtering target surface of 1-8, dross is not observed.
And, sputtering condition is set to, and sputtering pressure is 0.4Pa, and DC power is 100W, and substrate temperature is room temperature.In order to promote The generation of dross and add hydrogen in atmosphere gas.
Dross employs following method, i.e. amplify the target surface after 50 times of ground observation sputterings using stereomicroscope Change, to 3mm2The dross measurement number of more than 20 μm produced in the visual field is average.The dross number of generation is shown in table 1.
Comparative example 1 and 2
Except with the atomic ratio mixed material powder shown in table 1, with (800 DEG C to sintering of programming rate shown in table 1 Temperature), beyond sintering temperature, sintering time be sintered, manufacture identically with embodiment 1-8, have rated sintered body and sputtering Target.The results are shown in Table 1.
In the sputtering target of comparative example 1 and 2, paradoxical discharge is produced in sputtering, dross is observed on target surface.In addition, In the target of comparative example 1 and 2, In is observed2O3Bixbyite structure, InAlZn2O5And InAlZnO4Framework and Zn2SnO4Spinel structure.In2O3Bixbyite structure can be confirmed with card JCPDSNo.06-0416.
In2O3Bixbyite structure be present in the target of comparative example 1 and 2, sintering when in In2O3Cohesion part hair Raw exception grain growth, remaining pore, it is thus regarded that the overall density of sintered body is possible without improving.
In the sputtering target of comparative example 1 and 2, due to making programming rate (800 DEG C are arrived sintering temperature) more than 2 DEG C/min, therefore The relative density of target is less than 98%, and body resistivity is more than 5m Ω cm.
[table 1]
Embodiment 9-16
[film forming of oxide semiconductor thin-film]
In magnetic control sputtering device, 4 inches of targets of the composition shown in the table 2 and table 3 made in embodiment 1-8 are installed, Slide (Corning company system #1737) has been respectively mounted as substrate.Using DC magnetron sputtering methods, under conditions of following The amorphous film of thickness 50nm is formed on slide.
In film forming, Ar gas, O are imported with the intrinsic standoff ratio (%) shown in table 2 and table 32Gas and H2O gases.To be formed with non- The substrate of crystalloid film in an atmosphere, 300 DEG C heating 60 minutes and form oxide semiconductor thin-film.
Sputtering condition is as follows.
Substrate temperature：25℃
Reach pressure：8.5×10-5Pa
Atmosphere gas：Ar gas, O2Gas, H2O gases (partial pressure is with reference to table 2)
Sputtering pressure (gross pressure)：0.4Pa
Input electric power：DC100W
S (substrate)-T (target) distance：70mm
[evaluation of oxide semiconductor thin-film]
The substrate that oxide semiconductor thin-film will be formed with is arranged at ResiTest8300 types (Dongyang Technica companies System) in, Hall effect is have rated at room temperature.In addition, being analyzed using ICP-AES, contained each unit in confirmation sull The atomic ratio of element is identical with sputtering target.
In addition, have studied crystal structure using X-ray diffraction measure device (Rigaku Ultima-III).
In embodiment 9-16, film does not observe diffraction maximum after just piling up, and confirms as noncrystalline.In addition, in air Under carry out 300 DEG C × 60 minutes heat (annealing) after also do not observe diffraction maximum, confirm as noncrystalline.
The condition determination of XRD is as follows.
Device：(strain) Rigaku Ultima-III
X-ray：Cu-K α line (wavelengthUsing graphite monochromator monochromatization)
2 θ-θ bounce techniques, continuous scanning (1.0 °/minute)
Sampling interval：0.02°
Slit DS, SS：2/3°、RS：0.6mm
[manufacture of thin film transistor (TFT)]
As substrate, the electric conductivity silicon substrate of the heat oxide film with thickness 100nm has been used.Heat oxide film is exhausted as grid Velum plays a role, and electric conductivity silicon portion plays a role as grid.
On gate insulating film shown in table 2 and 3 under conditions of spatter film forming, produce the noncrystal membrane of thickness 50nm. OFPR#800 (Tokyo Applied Chemistry Industrial Co., Ltd.'s system), coating, prebake conditions (80 DEG C, 5 minutes), exposure are used as resist. After development, (120 DEG C, 5 minutes) are toasted after carrying out, etched using oxalic acid, be patterned as required shape.In hot-blast heater Carry out heating (annealing) in 60 minutes at 300 DEG C.
Thereafter, the film of Mo (100nm) is formed using spatter film forming, needed for using stripping method, source drain pattern is turned to Shape.As the treatment of the last stage of formation diaphragm as shown in table 2 and 3, an oxidation two is implemented to oxide semiconductor film Nitrogen plasma treatment, SiO is formed using plasma CVD method (PECVD)xFilm and as diaphragm.Opened using hydrofluoric acid If contact hole, thin film transistor (TFT) is produced.
To made thin film transistor (TFT), field-effect mobility (μ), S values and threshold voltage (Vth) are have rated.By these Result is shown in table 2 and 3.
Using Semiconductor Parameter Analyzer (Keithley Instruments Co. Ltd. system 4200SCS), in room temperature, hide These characteristic values are determined under luminous environment (in shielding box).
To made transistor, drain voltage (Vd) is set to 1V, gate voltage (Vg) is set to -15~20V in addition, evaluated Transmission characteristic.These results are shown in table 2 and 3.
Field-effect mobility (μ) is calculated according to linear mobility, is defined with the maximum of Vg- μ.
The experiment of DC deviated stresses has been carried out to made thin film transistor (TFT).In table 2 and 3, there is shown applying Vg=15V, The change of TFT transmission characteristic of the DC stress (at 80 DEG C of stress temperature) of Vd=15V before and after 10000 seconds.
The variation of the threshold voltage of the thin film transistor (TFT) of embodiment 9-16 is very small, it is known that it is difficult to be subject to the shadow of DC stress Ring.
Comparative example 3 and 4
Using the 4 inches of targets made in comparative example 1 and 2, processed according to the sputtering condition shown in table 3, heating (annealing) Condition and diaphragm form pre-treatment, make identically with embodiment 9-16, have rated oxide semiconductor thin-film and film crystalline substance Body pipe.The results are shown in Table 3.
As shown in table 2 and 3, it is known that the field-effect mobility of the element of comparative example 3 and 4 is less than 15cm2/ Vs, with embodiment The element of 9-16 is compared and is greatly lowered.In addition, the thin film transistor (TFT) of comparative example 3 and 4 DC deviated stresses experiment as a result, Threshold voltage changes more than 1V, it is known that produce the deterioration of significant characteristic.
[table 2]
[table 3]
Embodiment 17-19
According to the sputtering condition shown in table 4, annealing conditions, make identically with embodiment 9-16, have rated oxide Semiconductive thin film and thin film transistor (TFT).The results are shown in Table 4.In embodiment 17-19, substitution DC is sputtered and is utilized AC sputterings Implement film forming.
Above-mentioned AC sputterings are carried out using the device shown in the Fig. 1 disclosed in Japanese Unexamined Patent Publication 2005-290550 publications.
For example in embodiment 17, the 200mm wide, 1700mm long, the 6 target 31a of thickness 10mm that are made in embodiment 1 are used ~31f, each target 31a~31f is abreast configured with the width of substrate, and makes distance for 2mm.Magnetic field formation mechanism 40a The width of~40f is identical with target 31a~31f, is 200mm.
From gas supply system using as the Ar and H of sputter gas2O is directed respectively into system.Sputtering condition is set to 0.5Pa, the power of AC power is set to 3W/cm2(=10.2kW/3400cm2), frequency is set to 10kHz.Film forming under this condition 10 seconds, the thickness of the film obtained by measure was 12nm.Film forming speed is the high speed of 72nm/ minutes, is suitable for a large amount of productions.
The glass substrate that film will be formed with is put into electric furnace, 300 DEG C in atmosphere, the condition of 60 minutes (under air atmosphere) After lower heat treatment, with 1cm2Size cut out, carry out based on 4 sonde methods Hall determine.As a result, carrier concentration is 2.62×1017cm-3, can confirm that fully semiconductor transformation.In addition, confirming that film is amorphous after just piling up according to XRD determining Matter, 300 DEG C in atmosphere, after 60 minutes also be noncrystalline.In addition, be analyzed to identify according to ICP-AES, it is contained in sull Each element atomic ratio it is identical with the atomic ratio of sputtering used in film forming.
And, in embodiment 18 and 19, the target made in substitution embodiment 1 has used making in embodiment 4 and 6 respectively Target.
Comparative example 5
The target made in substitution embodiment 1,4 and 6, using the target made in comparative example 1, according to the sputtering shown in table 4 Condition, annealing conditions, make, have rated oxide semiconductor thin-film and thin film transistor (TFT) identically with embodiment 17-19.Will knot Fruit is shown in table 4.
As shown in table 4, the field-effect mobility of the element of comparative example 5 is less than 15cm2/ Vs, it is known that with embodiment 17-19 phases Than being greatly lowered.
[table 4]
Embodiment 20-29
[manufacture of thin film transistor (TFT)]
As substrate, the electric conductivity silicon substrate of the heat oxide film with thickness 100nm has been used.Heat oxide film is exhausted as grid Velum plays a role, and electric conductivity silicon portion plays a role as grid.Will carry heat oxide film electric conductivity silicon substrate 1ppm, The HCN aqueous solution (cleaning fluid) cleaning of the extremely low concentration of pH10.Temperature is set as 30 DEG C and is cleaned.
As embodiment 20-29, respectively using the target made in embodiment 1-8,1,2, according to splashing shown in table 5 and table 6 Condition, annealing conditions are penetrated, the noncrystal membrane of thickness 50nm is produced on gate insulating film.OFPR#800 has been used as resist (Tokyo Applied Chemistry Industrial Co., Ltd.'s system), coating, prebake conditions (80 DEG C, 5 minutes), exposure.After development, (120 are toasted after carrying out DEG C, 5 minutes), etched with oxalic acid, be patterned as required shape.Thereafter to the element of embodiment 20-26 in hot-blast heater Carry out heating (annealing) in 60 minutes at 450 DEG C, to the element of embodiment 27-29, carry out heating for 60 minutes at 300 DEG C Treatment (annealing).
Thereafter, the film of Mo (200nm) is formed using spatter film forming.Needed for using raceway groove etching, source drain pattern is turned to Shape.Thereafter, as the treatment of the last stage of formation diaphragm as shown in table 5 and 6, one is implemented to oxide semiconductor film Nitrous oxide corona treatment, SiO is formed using plasma CVD method (PECVD)xFilm and as diaphragm.Use hydrogen Fluoric acid opens up contact hole, produces the thin film transistor (TFT) of back of the body channel etch type.
To the channel layer of the thin film transistor (TFT) with diaphragm, section TEM (transmission electron microscopes are used； Transmission Electron Microscope) carry out the crystallinity evaluation based on electron beam diffraction figure.Device is used Hitachi field emission type transmission electron microscope HF-2100.
Channel layer to the element of embodiment 20-26 has carried out section tem analysis, as a result, front raceway groove side does not have Diffraction pattern is observed, is noncrystalline, and diffraction pattern is partly observed in back channel side, it is known that with the area for having crystallized Domain.On the other hand, for the element of embodiment 27-29, front raceway groove side, back channel side all do not observe diffraction pattern, confirm It is noncrystalline.
To manufactured transistor, drain voltage (Vd) is set to 1V, gate voltage (Vg) is set to -15~20V in addition, evaluated Transmission characteristic.During these results are shown in into table 5 and table 6.
Field-effect mobility (μ) is calculated according to linear mobility, is defined with the maximum of Vg- μ.
To made thin film transistor (TFT), the experiment of DC deviated stresses has been carried out.In table 5 and table 6, there is shown apply Vg= The change of TFT transmission characteristic of the DC stress (at 80 DEG C of stress temperature) of 15V, Vd=15V before and after 10000 seconds.
The variation of the threshold voltage of the thin film transistor (TFT) of embodiment 20-29 is very small, it is known that it is difficult to be subject to the shadow of DC stress Ring.
Comparative example 6 and 7
Also the electric conductivity silicon substrate with heat oxide film has been used in comparative example 6 and 7 identically with embodiment 20-29, so Without carrying out the cleaning by the HCN aqueous solution (cleaning fluid).
Using the target made in comparative example 1 and 2, according to the sputtering condition shown in table 6, annealing conditions, not to raceway groove Nitrous oxide corona treatment is carried out, in addition, made identically with embodiment 20-29, be have rated back of the body raceway groove etching Type thin film transistor (TFT).The results are shown in Table 6.
As shown in table 5 and 6, the field-effect mobility of the back of the body channel etch type thin film transistor (TFT) of comparative example 6 and 7 is less than 15cm2/ Vs, it is known that be greatly lowered compared with the back of the body channel etch type thin film transistor (TFT) of embodiment 20-29.
In addition, section tem analysis have been carried out to the channel layer of the element of comparative example 6 and 7, as a result, front raceway groove side, Back channel side does not all observe diffraction pattern, confirms as noncrystalline.
[table 5]
[table 6]
Industrial applicability
The thin film transistor (TFT) obtained using sputtering target of the invention can be as display device, especially as large area Display applications are used.
Although several embodiments of the present invention and/or embodiment are described in detail in described above, but this area skill Art personnel be easy to without materially departing from new enlightenment of the invention and effect to these implementation methods illustratively and/or Embodiment applies many changes.Thus, these many changes are contained in the scope of the present invention.
The content for turning into the basic Japanese publication specification of Paris priority of the application is all referred into this explanation In book.

Claims (42)

1. a kind of sputtering target, is formed by the oxide containing phosphide element In, tin element Sn, Zn-ef ficiency Zn and aluminium element Al,
It is included with InAlO3(ZnO)mThe framework compound of expression, and do not contain with In2O3The bixbyite structure of expression Compound, the m is 0.1~10, the atomic ratio of the phosphide element, tin element, Zn-ef ficiency and aluminium element meet following formula (1)~ (4)：
0.10≤In/(In+Sn+Zn+Al)≤0.30 (1)
0.01≤Sn/(In+Sn+Zn+Al)≤0.30 (2)
0.10≤Zn/(In+Sn+Zn+Al)≤0.65 (3)
0.01≤Al/(In+Sn+Zn+Al)≤0.30 (4)
In formula, In, Sn, Zn and Al represent the amount of substance of phosphide element in sputtering target, tin element, Zn-ef ficiency and aluminium element respectively.
2. sputtering target according to claim 1, wherein, the m is 0.5~7.
3. sputtering target according to claim 1 and 2, wherein, the m is 1~3.
4. sputtering target according to claim 1 and 2, wherein, the formula (2) for 0.05≤Sn/ (In+Sn+Zn+Al)≤ 0.25。
5. sputtering target according to claim 1 and 2, wherein, the formula (2) for 0.07≤Sn/ (In+Sn+Zn+Al)≤ 0.18。
6. sputtering target according to claim 1 and 2, wherein, the formula (3) for 0.25≤Zn/ (In+Sn+Zn+Al)≤ 0.60。
7. sputtering target according to claim 1 and 2, wherein, the formula (3) for 0.40≤Zn/ (In+Sn+Zn+Al)≤ 0.60。
8. sputtering target according to claim 1 and 2, wherein, the formula (4) for 0.02≤Al/ (In+Sn+Zn+Al)≤ 0.25。
9. sputtering target according to claim 1 and 2, wherein, the formula (4) for 0.02≤Al/ (In+Sn+Zn+Al)≤ 0.15。
10. sputtering target according to claim 1 and 2, wherein,
It is described with InAlO3(ZnO)mThe framework compound of expression is selected from InAlZn2O5The framework compound of expression And with InAlZnO4More than a kind in the framework compound of expression, the m is 0.1~10.
11. sputtering targets according to claim 1 and 2, it contains with Zn2SnO4The spinel structure compound of expression.
12. sputtering targets according to claim 1 and 2, its relative density is more than 98%.
13. sputtering targets according to claim 1 and 2, its relative density is more than 98.5%.
14. sputtering targets according to claim 1 and 2, its relative density is more than 99%.
15. sputtering targets according to claim 1 and 2, its specific insulation is below 5m Ω cm.
16. sputtering targets according to claim 1 and 2, its specific insulation is below 3m Ω cm.
17. sputtering targets according to claim 1 and 2, wherein, the maximum particle diameter of the crystal in the oxide for 8 μm with Under.
The manufacture method of the sputtering target any one of a kind of 18. claims 1~17, including phosphide element, tin unit will be contained The formed body of the oxide of element, Zn-ef ficiency and aluminium element is warmed up to sintering temperature from 800 DEG C for 0.1~2 DEG C/min with programming rate The operation spent and kept for 10~50 hours in the sintering temperature and sintered, the sintering temperature is 1200 DEG C~1650 DEG C Scope.
The manufacture method of the sputtering target any one of a kind of 19. claims 1~17, it includes following operation (1), operation (2) and operation (3),
Operation (1)：By the raw material containing phosphide element In, tin element Sn, Zn-ef ficiency Zn and the aluminium element Al for meeting following atomic ratios Compound mixing, the operation for shaping and being made formed body,
Operation (2)：Formed body sintering is made the operation of sintered body,
Operation (3)：The operation of sputtering target is made by processing the sintered body,
0.10≤In/(In+Sn+Zn+Al)≤0.30 (1)
0.01≤Sn/(In+Sn+Zn+Al)≤0.30 (2)
0.10≤Zn/(In+Sn+Zn+Al)≤0.65 (3)
0.01≤Al/(In+Sn+Zn+Al)≤0.30 (4)
In formula, In, Sn, Zn and Al represent the amount of substance of phosphide element, tin element, Zn-ef ficiency and aluminium element respectively.
The manufacture method of 20. sputtering targets according to claim 19, wherein,
The starting compound is the combination of indium oxide, tin oxide, zinc oxide and aluminum metal, or indium oxide, tin oxide, oxidation The combination of zinc and aluminum oxide.
The manufacture method of 21. sputtering target according to claim 19 or 20, wherein, the starting compound is powder.
The manufacture method of 22. sputtering target according to claim 19 or 20, wherein, starting compound is indium oxide, oxidation The mixed-powder of tin, zinc oxide and aluminum oxide.
The manufacture method of 23. sputtering targets according to claim 21, wherein, the average grain of the powder of the starting compound Footpath is 0.1 μm~1.2 μm.
The manufacture method of 24. sputtering targets according to claim 21, wherein, the average grain of the powder of the starting compound Footpath is 0.1 μm~1.0 μm.
The manufacture method of 25. sputtering target according to claim 19 or 20, it is included the formed body with programming rate 0.1~2 DEG C/min is warmed up to sintering temperature and the work for being kept for 10~50 hours in the sintering temperature and being sintered from 800 DEG C Sequence, the sintering temperature is 1200 DEG C~1650 DEG C of scope.
A kind of 26. oxide semiconductor thin-films, the sputtering target any one of its usage right requirement 1~17 utilizes sputtering method Film forming is formed.
27. a kind of manufacture methods of oxide semiconductor thin-film, containing selected from hydrone, oxygen molecule and nitrous oxide molecules In more than a kind and rare-gas atom mixed gas atmosphere under, usage right requirement 1~17 any one of splashing Shoot at the target and utilize sputtering film-forming.
The manufacture method of 28. oxide semiconductor thin-films according to claim 27, wherein,
The mixed gas are the mixed gas at least containing rare-gas atom and hydrone.
The manufacture method of 29. oxide semiconductor thin-films according to claim 28, wherein,
The ratio of contained hydrone is calculated as 0.1%~25% with intrinsic standoff ratio in the mixed gas.
The manufacture method of 30. oxide semiconductor thin-film according to any one of claim 27~29, wherein, it is described to splash Penetrate method and be selected from DC sputtering methods, RF sputtering methods, AC sputtering methods and pulse DC sputtering methods.
The manufacture method of 31. oxide semiconductor thin-film according to any one of claim 27~29, wherein, it is described to splash Partial pressure of oxygen ratio when penetrating film forming is 0% less than 40%.
The manufacture method of 32. oxide semiconductor thin-film according to any one of claim 27~29, wherein,
To the position facing with the sputtering target of more than 3 for being separated by the setting of the spacing parallel arranging of regulation in vacuum chamber, according to Secondary conveyance substrate, negative potential and positive potential are alternately applied by AC power to each target, and at least one is from the defeated of AC power Go out in the AC power branch that the target with more than 2 is connected, while apply the target of current potential between target more than 2 Switching, while make on target produce plasma and in substrate surface film forming.
The manufacture method of 33. oxide semiconductor thin-films according to claim 32, wherein,
The AC power density of the AC power is set to 3W/cm2Above and 20W/cm2Below.
The manufacture method of 34. oxide semiconductor thin-films according to claim 32, wherein,
The frequency of the AC power is 10kHz~1MHz.
The manufacture method of 35. oxide semiconductor thin-films according to claim 32, wherein, circulated in air atmosphere or oxygen Under atmosphere, further the sull that the utilization sputtering is obtained is kept for 15 minutes~5 hours and reality at 150~500 DEG C Apply annealing.
A kind of 36. thin film transistor (TFT)s, it has using the oxide semiconductor thin-film any one of claim 27~29 Manufacture method film forming oxide semiconductor thin-film as channel layer.
37. thin film transistor (TFT)s according to claim 36, its field-effect mobility is 15cm2/ more than Vs.
38. thin film transistor (TFT) according to claim 36 or 37, its S value is below 0.8V/dec.
39. thin film transistor (TFT) according to claim 36 or 37, its S value is below 0.3V/dec.
40. thin film transistor (TFT) according to claim 36 or 37, it is channel etch type.
A kind of 41. display devices, it possesses the thin film transistor (TFT) any one of claim 36~40.
42. display devices according to claim 41, its bottom gate with channel etch type is constituted.
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